Amino-Acid-Induced Circular Polarized Luminescence in One-Dimensional Manganese(II) Halide Hybrid

Circular polarized luminescence (CPL)-active materials attract great attentions owing to their widely applications in 3D optical displays and encrypted transmission. Inspired by the strategies adopted in perovskite based CPL materials, herein, CPL-active hybrids (D)- and (L)-(tert-butyl prolinate)MnCl₃ were successfully prepared by assembling chiral D/L tert-butyl prolinate with manganese (II) chloride. Single crystal structures show the as-formed hybrids possess one-dimensional (1D) structure containing linear chains of face-sharing MnCl₆ octahedral surrounded by prolinate cations. The 1D Mn(II) hybrids display strong red emission peaked at 646 nm with PLQY of 67.1 % and 57.2 % for d -type and l -type, respectively, representing the highest PLQY for 1D Mn^II hybrids. Interestingly, the 1D Mn(II) hybrids exhibit prominent circular dichroism (CD) signals and remarkable CPL activity with the dissymmetry factor g of 6.1*10⁻³ and −6.3*10⁻³ from 550 to 800 nm for (D)- and (L)-(tert-butyl prolinate)MnCl₃, respectively, owing to the existence of chiral cations. It is worthy noted the obtained g represents the highest value for non-lead organic–inorganic hybrids.     

Metal-Mediated Directional Capping of Rod-Packing Metal–Organic Frameworks

Two new rod-packing metal–organic frameworks (RPMOF) are constructed by regulating the in situ formation of the capping agent. In CPM-s7, carboxylate linkers extend 1D manganese-oxide chains in four additional directions, forming 3D RPMOF. The substitution of Mn²⁺ with a stronger Lewis acidic Co²⁺, leads to an acceleration of the hydrolysis-prone sulfonate linker, resulting in presence of sulfate ions to reduce two out of the four carboxylate-extending directions, and thus forming a new 2D rod-packing CPM-s8. Density functional theory calculations and magnetization measurements reveal ferrimagnetic ordering of CPM-s8, signifying the potential of exploring 2D RPMOF for effective low-dimensional magnetic materials.     

锌活化Fe/Co/N掺杂的生物质碳基高效氧还原催化剂

为了推动清洁能源-燃料电池的广泛应用, 迫切需要研发成本低、 原料来源广泛的过渡金属基高效氧还原反应(ORR)催化材料, 来替代目前使用的贵金属铂基催化材料. 本文以铁和钴等非贵金属离子作为催化材料的主要活性位点, 通过金属-羧基/羟基螯合键原位预锚定在具有三维(3D)孔道结构、 富含羧基和羟基以及极易在水溶液中形成凝胶网络的海洋生物质材料海藻酸钠上, 经冷冻干燥得到气凝胶; 然后通过高温碳化, 得到活性位点均匀分布在具有多级孔结构的碳骨架中的高活性、 高稳定的Co/Zn/Fe/N@bio-C-2氧还原催化剂材料, 该催化剂包含2种不同的铁基活性材料(Fe₂O₃和Fe)以及2种不同的钴基活性材料(CoO和Co).利用硝酸锌作为活化剂来改善催化材料的孔道结构, 使制备碳材料的总面积从149.3 m²/g增加到325.3 m²/g. 通过一系列对比实验发现, Fe/Co双活性位点与合适比表面积的协同作用使得Co/Zn/Fe/N@bio-C-2获得了最佳的ORR催化活性.其在0.1 mol/L KOH溶液中起始电位达到0.99 V, 半波电位可达0.87 V.     

Metallaphotoredox⁃Catalyzed O⁃Arylation of Serine北大核心CSCD

A metallaphotoredox catalyzed hydroxyl aromatization of serine is developed to achieve rapid synthesis of aryl ethers of various serine derivatives. Under the catalytic system of ethylene glycol dimethyl ether nickel bromide （NiBr2 （dme））/4,4'-dimethoxy-2,2'-bipyridine/zinc powder and synergistic iridium photoredox catalysis, nickel is catalyzed and inserted into the C—Br bond, and then followed by transmetalation with the hydroxyl group of serine. The resulting Ni（Ⅱ）species are oxidized by the excited Ir（Ⅲ）species to a Ni（Ⅲ）intermediate. This intermediate is unstable and reductive elimination takes place rapidly to give the target product O-arylated serine in the yields from 65% to 39%. Through a metallaphotoredox catalysis strategy,the reaction features mild,efficient,clean and broad scope of substrate, providing a new way for the synthesis of various serine derivatives with medicinal value. © 2022, Science Press (China). All rights reserved.     

发光铱(Ⅲ)配合物抗肿瘤活性研究及应用

铱(Ⅲ)配合物因其发光量子产率高且波长易调控、发光寿命长和光稳定性好的特点,在发光材料领域备受关注。铱(Ⅲ)配合物细胞渗透能力强,能靶向多种细胞组织并影响其结构和功能,表现出独特的抗肿瘤活性,是目前金属抗肿瘤药物特别是PDT光敏剂方向的研究热点。本文重点关注铱(Ⅲ)配合物的结构对其发光性能与抗肿瘤性能的影响,综述了近期铱(Ⅲ)配合物在生物成像、探针与传感、抗肿瘤诊疗等领域的研究进展,并对目前研究中存在的问题及其应用前景进行探讨和展望。     

钴铁水滑石基材料在电催化析氧中的应用

析氧反应(OER)是电催化裂解水、二次金属-空气电池和可再生燃料电池等绿色可持续能源储存和转化技术中的关键步骤,但其较高的势垒和迟滞的动力学过程限制了反应的效率。因此,设计开发高效、稳定的非贵金属催化剂是新能源领域面临的挑战之一。钴铁水滑石(CoFe LDH)材料具有独特的二维层状结构、丰富多变的化学组成、高分散的金属阳离子、优异的稳定性和成本低廉等优点,在OER反应中有广泛的应用前景。但不良的导电性和有限的活性位点阻碍了CoFe LDH的工业化应用。本文首先介绍了CoFe LDH的结构并阐述了其OER反应机理,接着总结了CoFe LDH的制备工艺,并详细综述了近年来提升其OER性能的改性策略：插层剥离、空位制造、材料复合、离子取代和衍生物等。最后讨论了水滑石材料现阶段存在的问题和未来在能源转化和利用领域的发展方向。     

基于扩散强化的Pickering界面生物催化系统构建及CO2矿化过程研究

CO₂的有效利用有助于解决环境和生态问题.碳酸酐酶(CA)等酶分子可精准活化CO₂分子以降低反应能垒,为CO₂的高效和高选择性转化提供了一种有前景的途径.然而,酶离开生物体后易失活,且难以重复利用.目前,包埋型固定化酶是常用且有效的提高酶稳定性与回用率的方法之一,但载体的存在会造成反应物CO₂内扩散阻力增加,降低反应活性.此外,CO₂酶促转化是一个气-液-固三相反应过程,反应体系中CO₂的外扩散性能也需要加强.金属有机骨架(MOFs),特别是咪唑酯骨架(ZIFs),常被用作酶固定化的载体.ZIFs的拓扑结构可被设计成不同形貌,进而通过ZIFs的结构工程来加强分子向其中的内扩散.Pickering乳液是指以固体颗粒代替常规表面活性剂而稳定的乳液.当固体颗粒具有催化活性时,催化剂颗粒会扩大液-液-固或气-液-固三相接触面积,从而有效协调反应物在不同相中的扩散时间.如果酶被用作这些颗粒的活性中心,所制备的Pickering乳液也可能具备类似的特性,可加强底物分子向酶的外扩散.本文选择两种具有不同结构的ZIFs(ZIF-L和ZIF-8),原位包埋CA后形成CA@ZIFs颗粒以稳定Pickeirng乳液.ZIF-L和CA@ZIF-L颗粒显示出独特的二维层状堆叠结构.ZIF-8和CA@ZIF-8颗粒呈棱角清晰的十二面体结构.与CA@ZIF-8颗粒相比,CA@ZIF-L颗粒显示出更大的孔径和更宽的孔径分布,这有助于CO₂从CA@ZIF-L颗粒表面扩散至酶活性中心.利用酶活测试来研究内扩散是否通过结构工程得到了加强,发现CA@ZIF-L颗粒的活性比CA@ZIF-8颗粒高22.3%,推测这是由于CA@ZIF-L颗粒特殊的十字花状结构会缩短CO₂从颗粒表面扩散至酶活性中心的距离.同时,十字花状结构可暴露更多的酶活性位点(CA@ZIF-L颗粒的暴露面积是CA@ZIF-8颗粒的~8倍),从而提升了反应物浓度并显示出更高的催化活性.本文还设计了吸附实验来进一步验证上述假设,发现BSA@ZIF-L颗粒对香豆素的吸附率远高于BSA@ZIF-8颗粒,说明与ZIF-8相比,酶包埋于ZIF-L具有更强的捕获小分子的能力,表明CO₂分子向CA@ZIF-L的扩散速度更快,即CA@ZIF-L的十字花状结构可强化系统的内扩散过程.进一步比较了PIBS和游离多酶体系的催化活性,将CO₂通入每个系统,在反应前20 min,PIBS的pH值下降速度比游离体系快得多,说明PIBS通过在气相和液相间构建更大的界面,缩短了CO₂向CA的扩散距离,从而提高了催化效率,促进了CO₂转化.上述假设也通过扩散动力学的计算得到了验证.为进一步研究PIBS的CO₂矿化能力,本文开展了CaCO₃矿化反应,发现PIBS的CaCO₃产量远高于游离多酶体系,表明构建的PIBS在强化内外扩散方面具有显著优势.最后,评估了PIBS在工业应用中的性能,由CA@ZIF-L和CA@ZIF-8颗粒构建的PIBS显示出较好的可回收性,在第8个循环后,PIBS仍可保持8.9 mg/5 min的CaCO₃产量.综上,PIBS可为CO₂的酶促转化和框架提供一个新方法和新平台.     

光催化甲苯衍生物、环烷烃与无机亚磺酸盐的位点选择性C(sp3)-H砜基化

烃类是最基础的有机分子之一,具有品种丰富、来源广泛、价格低廉等优势,其多样性、选择性转化一直备受合成化学家关注.然而,这些化合物中通常存在多个键能高、极性低、相互间差异性小的C(sp3)-H键,因此,实现高效、选择性C-H官能化极具挑战性.近年来,可见光催化广泛应用于有机合成中,与氢转移催化相结合所发展的可见光氢转移光...     

Cobalt Element Effect of Ternary Mesoporous Cerium Lanthanum Solid Solution for the Catalytic Conversion of Methanol and CO2 into Dimethyl Carbonate

A citric acid ligand assisted self-assembly method is used for the synthesis of ternary mesoporous cerium lanthanum solid solution doped with metal elements (Co, Zr, Mg). Their textural property was characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption-desorption, X-ray photoelectron spectroscopy and TPD techniques, and so on. The results of catalytic testing for synthesis of dimethyl carbonate (DMC) from CH₃OH and CO₂ indicated that the DMC yield reached 316 mmol/g on Ce-La-Co solid solution when the reaction temperature was 413 K and the reaction pressure was 8.0 MPa. It was found that Co had synergistic effect with La and Ce, doping of Co on the mesoporous Ce-La solid solution was helpful to increase the surface area of the catalyst, promote CO₂ adsorption and activation, and improve the redox performance of solid solution catalyst. The conversion of Co²⁺ to Co³⁺ resulted in the continuous redox cycle between Ce⁴⁺ and Ce³⁺, and the oxygen vacancy content of the catalyst was increased. Studies have shown that the catalytic performance of Ce-La-Co solid solution is positively correlated with oxygen vacancy content. On this basis, the reaction mechanism of DMC synthesis from CO₂ and CH₃OH on the catalyst was speculated.     

Mixed Quantum Classical Reaction Rates based on the Phase Space Formulation of the Hierarchical Equations of Motion

In a previous work [J. Chem. Phys. 140 , 174105 (2014)], we have shown that a mixed quantum classical (MQC) rate theory can be derived to investigate the quantum tunneling effects in the proton transfer reactions. However, the method is based on the high temperature approximation of the hierarchical equation of motion (HEOM) with the Debye-Drude spectral density, and results in a multi-state Zusman type of equation. We now extend this theory to include quantum effects of the bath degrees of freedom. By writing the full HEOM into a multidimensional partial differential equation in phase space, we can define a new reaction coordinate, and the previous method can be generalized to the full quantum regime. The validity of the new method is demonstrated by using numerical examples, including the spin-Boson model, and the double well model for proton transfer reaction. The new method is found to resolve some key problems of the previous theory based on high temperature approximation, including possible numerical instability in long time simulation and wrong rate constant at low temperatures.